2-Chloro-5-nitropyridine → Dibenzyl 5-nitro-2-pyridylmalonate

HRID 858065Notes

Reaction equation

CC(C)([O-])C.[K+].[C:7]([O:20][CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)(=[O:19])[CH2:8][C:9]([O:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:10].Cl[C:29]1[CH:34]=[CH:33][C:32]([N+:35]([O-:37])=[O:36])=[CH:31][N:30]=1>CS(C)=O>[CH2:12]([O:11][C:9](=[O:10])[CH:8]([C:29]1[CH:34]=[CH:33][C:32]([N+:35]([O-:37])=[O:36])=[CH:31][N:30]=1)[C:7]([O:20][CH2:21][C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1)=[O:19])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

Conditions

Temperature: 95 °C

Procedure

A solution of potassium tert-butoxide in dimethylsulfoxide was treated with dibenzyl malonate. This mixture was stirred at 95° C. for 10 min. At this time, the reaction was treated with a solution of 2-chloro-5-nitropyridine. The resulting mixture was stirred at 95° C. for 1.5 h. At this time, the reaction mixture was poured into ice/water and extracted with ethyl acetate. The organics were washed with a saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered, and concentrated in vacuo. Flash chromatography (Merck Silica gel 60, 230–400 mesh, 20/80 ethyl acetate/hexanes) afforded 2-(5-nitro-pyridin-2-yl)-malonic acid dibenzyl ester (45%) as a bright yellow solid; LRMS for C22H18N2O6 (M−H)+ at m/z=405.

Workup

stirringThe resulting mixture was stirred at 95° C. for 1.5 h
extractionextracted with ethyl acetate
washThe organics were washed with a saturated aqueous sodium chloride solution
dry with materialdried over sodium sulfate
filtrationfiltered
concentrationconcentrated in vacuo

Sources & evidence

ORD record: ord-5868b58aa5fc487bb5fd02bd9d65b45b
Source dataset: uspto-grants-2006_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07148229B2

Reaction notes

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